CN102702028B - Method for synthesizing methacryloxyethyl isocyanate - Google Patents
Method for synthesizing methacryloxyethyl isocyanate Download PDFInfo
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- CN102702028B CN102702028B CN 201210191521 CN201210191521A CN102702028B CN 102702028 B CN102702028 B CN 102702028B CN 201210191521 CN201210191521 CN 201210191521 CN 201210191521 A CN201210191521 A CN 201210191521A CN 102702028 B CN102702028 B CN 102702028B
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- methylacryoyloxyethyl
- isocyanic ester
- thanomin
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Abstract
The invention discloses a method for synthesizing methacryloxyethyl isocyanate. The method comprises the following steps of: salifying ethanolamine serving as an initial raw material with hydrogen chloride or hydrochloric acid in an organic solvent, performing a condensation reaction with methacryloyl chloride under the action of an organic alkali catalyst to obtain methacryloxyethyl amidohydrochloride; introducing phosgene into the methacryloxyethyl amidohydrochloride for reacting to generate a methacryloxyethyl isocyanate solution; and performing reduced pressure desolvation and reduced pressure rectification on the methacryloxyethyl isocyanate solution in the presence of a polymerization inhibitor to obtain a methacryloxyethyl isocyanate product. The method has the advantages of simple process, low production cost, high product purity and high yield.
Description
Technical field
The present invention relates to a kind of synthetic method of methylacryoyloxyethyl isocyanic ester.
Background technology
Methylacryoyloxyethyl isocyanic ester (MOI) claims again methacrylic acid isocyano-ethyl ester, 2-methyl-2-propylene-2-isocyanato ethyl, it is a kind of novel fine chemistry industry novel material, because it contains isocyanic ester and methacrylic acid gene, reactwity of monomer is high, and the difference in functionality compound is more easily solidified with visible light, ultraviolet ray and electron beam exposure the time.Monomer whose has been widely used in various electronic applications, as liquid photo-resist, film photo-resist and tackiness agent etc., and at sensitive materials, liquid-crystal display, and have application widely on various electronic original parts.
Domestic more existing R﹠D institutions have carried out the study on the synthesis of synthetic or its intermediate of this product; but gordian technique bottleneck end can be broken through: because of carbon in the methylacryoyloxyethyl isocyanic ester, carbon pair keys, isocyanic acid ester bond very active; carbon, the two keys of carbon are easily with hydrogenchloride generation addition reaction; the side reactions such as polymerization, carbonization easily occur in carbon, the two keys of carbon, isocyanate groups under high temperature when rectifying simultaneously, and product yield is low, content is low, be difficult to separation and purification.
Therefore, how solving the synthetic middle the problems referred to above that exist of methylacryoyloxyethyl isocyanic ester (MOI) is problems that those skilled in the art study always.
Summary of the invention
The object of the present invention is to provide the synthetic method of the methylacryoyloxyethyl isocyanic ester that a kind of technique is simple, production cost is low, product purity is high, yield is high.
Technical solution of the present invention is:
A kind of synthetic method of methylacryoyloxyethyl isocyanic ester is characterized in that: comprise the following steps:
(1) take thanomin as starting raw material, with hydrogenchloride or hydrochloric acid salify, and make methylacryoyloxyethyl amido hydrochloride with the methacrylic chloride condensation reaction under the organic alkali catalyst effect in organic solvent;
(2) pass into phosgene reaction generation methylacryoyloxyethyl isocyanate solution in methylacryoyloxyethyl amido hydrochloride;
(3) the methylacryoyloxyethyl isocyanate solution under stopper exists, gets the methylacryoyloxyethyl isocyanate products through decompression precipitation, rectification under vacuum.
Described organic solvent is any one in toluene, dimethylbenzene, chlorobenzene, ethylene dichloride, tetracol phenixin, and the consumption of organic solvent is 3～10 times of thanomin quality.
Described organic alkali catalyst is pyridine, triethylamine, DMA or 4-dimethylamino pyridine, and catalyst levels is 1%～5% of thanomin quality.
The consumption of methacrylic chloride is 1～3 times of thanomin (I) molar mass, and temperature of reaction is 20 ℃～110 ℃, 2～8 hours reaction times.
The phosgene consumption is 1～5 times of thanomin molar mass, and temperature of reaction is 40 ℃～120 ℃, 2～10 hours reaction times.
Pass into nitrogen after photochmeical reaction is complete, remove remaining phosgene and hydrogen chloride gas.
Described stopper is Resorcinol, p methoxy phenol, thiodiphenylamine, beta-phenyl naphthylamines, p-ten.-butylcatechol, cuprous chloride or iron trichloride.
The quality that adds stopper is 1%～5% of thanomin quality.Rectification under vacuum pressure is 1mmHg～10mmHg.
The present invention has following characteristics:
1, make catalyzer with 4-dimethyl amine yl pyridines in methacrylic chloride and ethanolamine hydrochloric salt condensation, logical photoreduction process, reduce condensation, logical photoresponse temperature, the hydrogenchloride of anti-blocking, carbon double-bond polymerization and generation and carbon, the two key generation addition reactions of carbon.
2, adopt during methylacryoyloxyethyl isocyanic ester (MOI) rectifying and add the stopper thiodiphenylamine and adopt the continuous rectification technology, effectively controlled the isocyanate groups high temperature polymerization, product yield is high, purity is high.Product yield reaches 90%(in thanomin), purity is more than 99%.
The invention will be further described below in conjunction with embodiment.
Embodiment
Embodiment 1
(1) drop into toluene 500ml, thanomin 61g(I in the 1000ml four-hole boiling flask) (1.0mol).Pass into while stirring hydrogen chloride gas to saturated.Get ethanolamine hydrochloric salt (II) toluene suspension liquid.
(2) add 4-dimethyl amine yl pyridines 2g in ethanolamine hydrochloric salt (II) the toluene suspension liquid of above-mentioned preparation, 40 ℃～50 ℃ of holding temperatures, drip methacrylic chloride 125g, drip off rear insulation reaction 2～3 hours, reaction finishes, then passes into phosgene with the speed of 1200ml/min～1400 ml/min, 40 ℃～50 ℃ of logical light temperature, logical light is after 2 hours, and the material clear that becomes stops logical phosgene.Pass into nitrogen rush residual phosgene and hydrogen chloride gas, get methylacryoyloxyethyl isocyanic ester (MOI) toluene liquid.Side reaction 3-chloromethyl-2-methylacryoyloxyethyl isocyanate content 0.8%.
(3) add thiodiphenylamine 1.5g in methylacryoyloxyethyl isocyanic ester (MOI) the toluene liquid of above-mentioned preparation, keep below pressure 20mmHg, on one side charging distill on one side, toluene is deviate from continuous still battery.
(4) in the rectifying tower of reflux ratio is housed, add methylacryoyloxyethyl isocyanic ester (MOI) crude product of above-mentioned preparation on one side, rectifying on one side, keep pressure 5mmHg, control input and output material speed, continuous rectification, collect 82～85 ℃ of fractions, obtain methylacryoyloxyethyl isocyanic ester (MOI) 140g, content 99.5%, yield 90.3%(in thanomin, do not roll over hundred).
Embodiment 2
The thanomin salify is with the step (1) of embodiment 1
(2) drip methacrylic chloride 125g in ethanolamine hydrochloric salt (II) toluene suspension liquid, keep 80 ℃～85 ℃ of dropping temperatures, after dripping off at this temperature insulation reaction 2～3 hours, reaction finishes, speed with 1200ml/min～1400 ml/min passes into phosgene again, 80 ℃～85 ℃ of logical light temperature, and logical light is after 2 hours, the material clear that becomes stops logical phosgene.Pass into nitrogen rush residual phosgene and hydrogen chloride gas, get methylacryoyloxyethyl isocyanic ester (MOI) toluene liquid.Side reaction 3-chloromethyl-2-methylacryoyloxyethyl isocyanate content 8.6%.
Precipitation, rectifying be with step (3), (4) of embodiment 1, gained methylacryoyloxyethyl isocyanic ester (MOI) 127g, content 97%, yield 82%(in thanomin, do not roll over hundred).
Embodiment 3
Salify, condensation, logical light are with step (1), (2) of embodiment 1
Decompression piptonychia benzene, rectifying time end adds the stopper thiodiphenylamine, and working method is with step (3), (4) of embodiment 1, gained methylacryoyloxyethyl isocyanic ester (MOI) 120g, content 98.5%, yield 77.4%(in thanomin, do not roll over hundred).
Embodiment 4
Salify, condensation, logical light are with step (1), (2) of embodiment 1
When toluene distillation and methylacryoyloxyethyl isocyanic ester (MOI) rectifying, in the disposable input rectifying of material pot, adopt gap rectifying, keep pressure 5mmHg, collect 82～85 ℃ of fractions, methylacryoyloxyethyl isocyanic ester (MOI) 123g, content 98.2%, yield 79.4%(in thanomin, do not roll over hundred).
In sum, embodiment 2 compares with embodiment 1: the end adds catalyzer 4-dimethylamino pyridine in condensation, logical light reaction procedure, reactive behavior is low, temperature of reaction is high, carbon, the two keys of carbon more easily occur with hydrogenchloride addition side reaction, by product 3-chloromethyl-2-methylacryoyloxyethyl isocyanate content is high, and products obtained therefrom methylacryoyloxyethyl isocyanic ester (MOI) yield, quality are all lower; Embodiment 3 compares with embodiment 1: the end adds the stopper thiodiphenylamine in precipitation, rectifying, causes carbon, the two keys of carbon and isocyanate groups high temperature polymerization, carbonization, and products obtained therefrom methylacryoyloxyethyl isocyanic ester (MOI) yield is lower; Embodiment 4 compares with embodiment 1: adopt the gap rectification method in precipitation, rectifying, in the disposable input precipitation of crude product, rectifying pot, in rectifying, methylacryoyloxyethyl isocyanic ester (MOI) is subjected to decoct (molten the frying in shallow oil) of high temperature long period, the side reactions such as polymerization, carbonization more easily occur, and products obtained therefrom methylacryoyloxyethyl isocyanic ester (MOI) yield is lower, content is low.
Claims (6)
1. the synthetic method of a methylacryoyloxyethyl isocyanic ester is characterized in that: comprise the following steps:
(1) take thanomin as starting raw material, with hydrogenchloride or hydrochloric acid salify, and make methylacryoyloxyethyl amido hydrochloride with the methacrylic chloride condensation reaction under the organic alkali catalyst effect in organic solvent;
(2) pass into phosgene reaction generation methylacryoyloxyethyl isocyanate solution in methylacryoyloxyethyl amido hydrochloride;
(3) the methylacryoyloxyethyl isocyanate solution under stopper exists, gets the methylacryoyloxyethyl isocyanate products through decompression precipitation, rectification under vacuum;
Described organic alkali catalyst is the 4-dimethylamino pyridine, and catalyst levels is 1%～5% of thanomin quality; Described stopper is thiodiphenylamine.
2. the synthetic method of methylacryoyloxyethyl isocyanic ester according to claim 1, it is characterized in that: described organic solvent is any one in toluene, dimethylbenzene, chlorobenzene, ethylene dichloride, tetracol phenixin, and the consumption of organic solvent is 3～10 times of thanomin quality.
3. the synthetic method of methylacryoyloxyethyl isocyanic ester according to claim 1 and 2, it is characterized in that: the consumption of methacrylic chloride is 1～3 times of thanomin molar mass, temperature of reaction is 20 ℃～110 ℃, 2～8 hours reaction times.
4. the synthetic method of methylacryoyloxyethyl isocyanic ester according to claim 1 and 2, it is characterized in that: the phosgene consumption is 1～5 times of thanomin molar mass, temperature of reaction is 40 ℃～120 ℃, 2～10 hours reaction times.
5. the synthetic method of methylacryoyloxyethyl isocyanic ester according to claim 1 and 2, is characterized in that: pass into nitrogen after photochmeical reaction is complete, remove remaining phosgene and hydrogen chloride gas.
6. the synthetic method of methylacryoyloxyethyl isocyanic ester according to claim 1 and 2, it is characterized in that: the quality that adds stopper is 1%～5% of thanomin quality, rectification under vacuum pressure is 1mmHg～10mmHg.
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| CN 201210191521 CN102702028B (en) | 2012-06-12 | 2012-06-12 | Method for synthesizing methacryloxyethyl isocyanate |
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| CN 201210191521 CN102702028B (en) | 2012-06-12 | 2012-06-12 | Method for synthesizing methacryloxyethyl isocyanate |
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| CN102702028B true CN102702028B (en) | 2013-11-06 |
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| CN103113261A (en) * | 2013-01-21 | 2013-05-22 | 张家港瀚康化工有限公司 | Preparation method of metharcylic acid, 2-isocyanatoethyl ester |
| CN103193675A (en) * | 2013-03-26 | 2013-07-10 | 浙江同丰医药化工有限公司 | Method for preparing ethyl methacrylate isocyanate |
| CN114929668A (en) * | 2020-01-06 | 2022-08-19 | 昭和电工株式会社 | (meth) acrylate compound having isocyanate group and method for producing same |
| CN116023301A (en) * | 2022-12-21 | 2023-04-28 | 浦拉司科技（上海）有限责任公司 | Synthetic method of isocyanate ethyl acrylate |
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| US2340757A (en) * | 1935-05-02 | 1944-02-01 | Heberlein Patent Corp | Isocyanates and related substances and process for their manufacture |
| US2679530A (en) * | 1949-11-04 | 1954-05-25 | Ciba Ltd | Process for the manufacture of alpha:beta-unsaturated carboxylic acid esters from beta-halogen carboxylic acid esters |
| US2718516A (en) * | 1952-11-08 | 1955-09-20 | Rohm & Haas | Isocyanato esters of acrylic, methacrylic, and crotonic acids |
| US2821544A (en) * | 1954-04-26 | 1958-01-28 | Bayer Ag | Production of alkylisocyanate esters of 2-alkenoic acids |
| US4278809A (en) * | 1977-06-15 | 1981-07-14 | The Dow Chemical Company | Process for preparing 2-isocyanatoalkyl esters of organic carboxylic acids |
| CN1125718A (en) * | 1994-03-22 | 1996-07-03 | 三井东压化学株式会社 | Process for the preparation of aliphatic polyisocyanates |
Family Cites Families (4)
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| JPH0749413B2 (en) * | 1987-08-10 | 1995-05-31 | 昭和電工株式会社 | Purification method of unsaturated carboxylic acid isocyanatoalkyl ester |
| JP2632977B2 (en) * | 1988-11-10 | 1997-07-23 | 昭和電工株式会社 | Method for producing unsaturated carboxylic acid-2-isocyanatoalkyl ester |
| JP2632984B2 (en) * | 1988-11-29 | 1997-07-23 | 昭和電工株式会社 | Process for producing unsaturated carboxylic acid isocyanatoalkyl ester |
| WO2005092842A1 (en) * | 2004-03-25 | 2005-10-06 | Showa Denko K.K. | Method for producing (meth)acrylate derivative having isocyanate group |
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2012
- 2012-06-12 CN CN 201210191521 patent/CN102702028B/en active Active
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|---|---|---|---|---|
| US2340757A (en) * | 1935-05-02 | 1944-02-01 | Heberlein Patent Corp | Isocyanates and related substances and process for their manufacture |
| US2679530A (en) * | 1949-11-04 | 1954-05-25 | Ciba Ltd | Process for the manufacture of alpha:beta-unsaturated carboxylic acid esters from beta-halogen carboxylic acid esters |
| US2718516A (en) * | 1952-11-08 | 1955-09-20 | Rohm & Haas | Isocyanato esters of acrylic, methacrylic, and crotonic acids |
| US2821544A (en) * | 1954-04-26 | 1958-01-28 | Bayer Ag | Production of alkylisocyanate esters of 2-alkenoic acids |
| US4278809A (en) * | 1977-06-15 | 1981-07-14 | The Dow Chemical Company | Process for preparing 2-isocyanatoalkyl esters of organic carboxylic acids |
| CN1125718A (en) * | 1994-03-22 | 1996-07-03 | 三井东压化学株式会社 | Process for the preparation of aliphatic polyisocyanates |
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